Noncatalytic condensation of aromatic compounds with unsaturated hydrocarbons



United States Patent NON CATALYTIC CONDENSATION OF AROMATIC COR [POUNDS WITH UNSATURATED HYDRO- CARBONS Vladimir N. Ipatiefi deceased, late of Chicago, 111., by Vladimir Haensel, Hinsdale, Herman Pines, Chicago, and Vincetta Kibort, Chicago, 111., executors, and Herman Pines and Bruno Kvetinskas, Chicago, Ill., assignors to Universal Gil Products Company, Des Plaines, 111., a corporation of Delaware No Drawing. Application July 27, 1953, Serial No. 370,611

20 Claims, (Cl. 260668) This application is a continuation-in-part of my copending application Serial No. 152,991, filed March 30, 1950, now abandoned.

This invention relates to the condensation of unsaturated hydrocarbons with aromatic compounds, and to the products and derivatives of products thereby produced. It is more particularly concerned with the conensation of unsaturated hydrocarbons with carbocyclic or heterocyclic aromatic ring compounds having attached to a nuclear carbon atom, a saturated carbon atom to which is attached at least one hydrogen atom.

The condensation of aromatic compounds with unsaturated hydrocarbons, such as the alkylation of arcmatic hydrocarbons with olefins, has been the subject of extensive investigations over a considerable period of time. These investigations have led to the discovery of various catalysts of one type or another to induce the reaction and to aid the selectivity thereof. In these re actions, up to a very recent time, nuclear condensation was all that was effected. For example, in the catalytic alkylation of aromatic compounds having attached to a carbon atom of the ring a saturated carbon atom to which is attached at least one hydrogen atom, the alkylation being carried out in the presence of an alkylation catalyst, the entering alkyl group carbon atom attaches to the aromatic nucleus. Very recently it has been shown that in the presence of metallic sodium, the alkyl group is introduced into the side chain. This latest step forward in the art, however, suffers from certain inherent disadvantages. First of all, the catalyst, sodium, is difficult to handle and tends to form complexes with the unsaturated hydrocarbons utilized, which complexes are pyrophoric and in some instances explosive in character. Furthermore, sodium is at the present time a relatively expensive chemical. Sodium also sufiers from the disadvantage that it becomes rapidly deactivated when used as a catalyst and thus, commercially, catalyst costs become exorbitant. It is necessary to use relatively large amounts of this catalyst over fairly short periods of time to obtain satisfactory yields of side chain alkylated products. When utilized, pressures from about 50 to about 3,000 atmospheres and temperatures from about 150 to 450 C. are common. The high cost and difiiculty in handling sodium as a catalyst are overcome by utilization of the process of the present invention. Furthermore, the art of using sodium is limited to the use of ethylene as the only operable olefin. Our invention is widely applicable to many various unsaturates as will be hereinafter set forth. We have invented a method of accomplishing side chain alkylation in which a catalyst is no longer necessary. Furthermore, we can carry out this noncatalytic reaction with little or no formation of carbon or other undesirable materials, and thus operate in a continuous manner. Surprisingly, this noncatalytic reaction can be carried out at temperatures and pressures within the range heretofore specified for the use of a side chain alkylation catalyst, namely, sodium. Thus,

2,758,140 Patented Aug. 7, 1956 we have found that at pressures over about 67 atmospheres, and at temperatures from about 350-500 C., and at hourly liquid space velocities of from about 0.1 to about 10, side chain alkylation takes place in good yields and with negligible or no carbon formation. This lack of carbon formation is not only interesting, but makes this process economically feasible when coupled with the conditions utilized and the yields of products obtained. It has also been demonstrated that thermal reactions in a high pressure autoclave, a batch process, such as between toluene and amylenes, result in the formation of large amounts of carbon. It is indeed surprising, as we have found, that when the reaction is carried out under temperature and pressure conditions in which a catalyst was formerly utilized, and in continuous manner, that there is no carbon formation. Thus, our invention must proceed through different steps than shown in the prior art.

It is an object of this invention to condense an unsaturated hydrocarbon with an aromatic compound selected from the group consisting of carbocyclic and heterocyclic ring compounds having attached to a nuclear carbon atom, a saturated carbon atom to which is attached at least one hydrogen atom.

It is another object of this invention to condense, in the absence of added catalyst, an unsaturated hydrocarbon with an aromatic compound selected from the group consisting of carbocyclic and heterocyclic ring compounds having attached to a nuclear carbon atom, a saturated carbon atom to which is attached at least one hydrogen atom.

Still another object is to noncatalytically condense a hydrocarbon selected from the group consisting of olefinic and acetylenic hydrocarbons, with an aromatic hydrocarbon possessing a side chain, said side chain containing an alpha carbon atom to which is attached a hydrogen atom.

A further object of this invention is to provide a process for the side chain alkylation of alkylaromatic hydrocarbons.

A still further object of this invention is to provide a method for producing aromatic compounds containing long straight hydrocarbon side chains, said compounds being useful in the production of detergents, wetting agents, and the like.

In a broad aspect, our invention comprises condensing an unsaturated hydrocarbon with an aromatic compound, particularly an aromatic compound having attached to the nucleus-a saturated carbon atom to which is attached at least one hydrogen atom, in the absence of added catalyst. This condensation is effected by compressing in the adsence of external heating, an aromatic compound and an unsaturated hydrocarbon to superatmospheric pressures, and thermally and noncatalytically reacting said compounds. We sometimes refer to this type of reaction as thermal condensation or thermal alkylation. Our invention also includes the preparation of alkylaromatic compounds of particular structural configurations, useful per se or as starting materials for the preparation of various other chemical substances.

In a broad embodiment, our invention relates to a process which comprises noncatalytically reacting an unsaturated hydrocarbon with an aromatic compound selected from the group consisting of carbocyclic and heterocyclic aromatic ring compounds having attached to a nuclear carbon atom, a saturated carbon atom to which is attached at least one hydrogen atom at condensation conditions.

In a more specific embodiment our invention relates to a process for producing a side chain alkylated aromatic compound which comprises compressing, in the absence of external heating, an unsaturated hydrocarbon and an aromatic compound selected from the group consisting of carbocyclic and heterocyclic ring compounds having attached to a nuclear carbon atom, a saturated carbon atom to which is attached at least one hydrogen atom, the moi ratio of aromatic compound to unsaturated hydrocarbon .being greater than about 1.0, thereafter theremally and R M PR 1';

where A represents an aromatic radical having a carbocyclic nucleus and R represents hydrogen or an organic radical attached to the indicated alpha carbon atom through a saturated carbon atom, with a compound selected from the group consisting of olefinic and acetylenic hydrocarbons at condensation conditions, the condensation conditions including compressing, in the absence of external heating, said reactants, containing a molar excess of aromatic compounds thereafter thermally and noncatalytically subjecting said compounds to reaction at a pressure greater than about 1,000 p. s. i., at a temperature from about 350 to about 500 C., and at an hourly liquid space velocity from about 0.1 to about 10, to efiect condensation of the unsaturated hydrocarbon with the carbocylic aromatic compound at said saturated carbon atom.

In still another embodiment, our invention relates to a process for producing side chain alkylated aromatic hydrocarbons which comprises compressing, in the absence of external heating, an unsaturated hydrocarbon and an alkylaromatic hydrocarbon having a hydrogen atom attached to the alpha carbon atom, said mixtue containing a molar excess of the alkylaromatic hydrocarbons, thereafter thermally and noncatalytically reacting said unsaturated hydrocarbon with the alkylarornatic hydrocarbon at the saturated carbon atom at a pressure greater than about 1,000 p. s. i., at a temperature of from about 350 to about 500 C., and at an hourly liquid space velocity from about 0.1 to about 10, and thereafter recovering the side chain alkylated resultant products.

The compounds with which unsaturated hydrocarbon atoms are condensed in our process comprise aromatic compounds having attached to a nuclear carbon atom a saturated carbon atom to which is attached at least one hydrogen atom. By the term aromatic compound we mean to include not only alkylbenzene, alkylnaphthalenes, and derivatives thereof, but also all compounds containing a stable ring or nucleus such as is present in benzene, and which possess unsaturation in the sense that benzene does. Consequently, it can be seen that the term aromatic compound, in the sense in which it is used in the specification and appended claims, not only includes carbocyclic compounds, but also hereterocyclic compounds having stable nuclei. The carbocyclic compounds may have a benzene, naphthalene, anthracene, etc., nucleus and the heterocyclic aromatic ring compounds contemplated for use in our process may contain both a carbocyclic and a heterocyclic ring such as is found in indole and carbazole. Also, the aromatic compounds may contain both a benzene nucleus and a cycloalkane nucleus such as is found in tetralin and in indan.

As hereinbefore stated, the aromatic compounds preferred for use in our process, contain a side chain attached to a nuclear carbon atom by a saturated carbon atom, i. e., a carbon atom that is bonded by univalent bonds to four atoms or groups. The saturated carbon atom should have at least one hydrogen atom attached thereto. These requisites are desirable for the reason that aromatic compounds such as tert-butylbenzene, which does not have a hydrogen atom attached to the alpha carbon atom, shows very little tendency under the conditions of operation employed in our process to undergo condensation of the type herein taught. Similarly, styrene, in which the alpha carbon atom in the side chain is unsaturated, does not condense with the unsaturated hydrocarbons in the manner herein specified. Thus the preferred aromatic compounds are those in which the alpha carbon atom of the side chain is saturated, and in which said saturated alpha carbon atom has at least one hydrogen atom attached thereto. The chain may comprise only one carbon atom as the methyl group in toluene, or it may comprise a number of carbon atoms in straight chain or branched chain relation such as the n-butyl radical or the isobutyl radical in n-butylbenzene and isobutylbenzene, respectively. The chain need not necessarily be an aliphatic chain; it may be a cycloalkane ring such as in tetralin or indan or as in cyclohexylbenzene.

Suitable alkylaromatic hydrocarbons include toluene, ethylbenzene, n-propylbenzene, cumene, normal, iso, and secondary butylbenzene, methylnaphthalene, and the like. Other suitable aromatic hydrocarbons include tetralin, indan, diphenylmethane, cyclopentylbenzene, cyclohexylbenzene, and methyl ethylbenzene.

The aromatic ring in the compounds herein referred to may contain other substituents such as a halo group, an alkoxy group such as methoxy and ethoxy, a nitro group, etc., in addition to containing one or more suitable aliphatic substituents.

The aromatic reactants employed in our process are condensed with unsaturated hydrocarbons. Two preferred classes of unsaturated hydrocarbons comprise organic hydrocarbons containing an ethylenic group and organic hydrocarbons containing an acetylenic group. For the purpose of our invention, aromatic compounds such as benzene are not regarded as being unsaturated. Examples of unsaturated hydrocarbons suitable for use in our process include olefins such as ethylene, propylene, l-butene, 2- butene, isobutylene, l-octene, l-decene, l-dodecene, propylene tetramer, nonenes, etc.; dienes such as butadiene, isoprene, and allene, etc.; polyolefins' containing more than two pairs of double bonds per molecule; .cycloolefins, and cyclodienes, such as cyclopentene, cyclohexene, methylcyclohexene, cyclopentadiene, etc.; and acetylenic hydroarbons such as acetylene, methylacetylene, phenylacetylene, and the like.

The combination of condensation conditions, including compressing the reactants in the absence of external heating and then thermally and noncatalytically subjecting said reactants to an elevated pressure and temperature, at specific space velocities are important variables in our process. When the process is carried out, for example, by sealing the reactants in a high pressure autoclave followed by heating to the desired temperature, large amounts of carbon are formed. In such a process, the pressure developed is dependent solely on the temperature utilized, the mol fractions of reactants present, and the internal volume of the autoclave utilized. It is readily apparent that in such an operation, the reactants are in contact over a wide pressure and temperature range as the heating up and cooling down process is carried out prior to reaching the desired temperature and pressure level, and following the period at the desired temperature and pressure level. In carrying out the process of our invention, the reactants are compressed to our desired superatmospheric pressure level, then contacted and thermally reacted with one another at the pressure which has been previously established. During compression, thereactants are not subjected to any external heating,v and their temperature will be substantially that of the atmosphere plus any heat added tothem by and during the compression stage. Further, during this compression stage, the heat added to them by compression may be lost by heat exchange with the atmosphere.

Pressure itself is one of the important variables of our ensues. The temperature and the hourly liquid space velocity utilized are inversely proportional to a certain extent. Hourly liquid space velocities from about 0.1 to about are generally preferred, although higher or process. By obtaining and maintaining the proper pres- 5 lower space velocities may be utilized. At a specific sure, substantially no carbon formation during the reactemperature, a decrease in the space velocity W111 cause tion is encountered. The condensation reactions with an increase in yields. Conversely, at a specific temperwhich our invention is concerned, ordinarily proceed with ature, an increase in space velocity w1ll cause a decrease the best yields when conducted at substantially superatin yields. mospheric pressure. We have obtained excellent results 10 Additlonal details and advantages of our lnventlon Wlll in the range of 1,000 to 12,000 pounds per square inch. be apparent from the following examples WhlCh are given In a continuous process, such as has now been demonfor the purposes of illustration and not for purposes of strated by the process of our invention, the desired preshmrtatron. The contlnuous type experiments listed 1n the sure level can be maintained, by the utilization of suitexamples were carried out in a hlgh pressure laboratory able pressure controlling instruments and valves. Such flow apparatus slmltal' to that described 111 Industrial and pressure controlling instruments may be air driven, elec- Englneeflng Chemistry, Volume 40, Startlhg on P 2059- trically driven, etc. In some instances, pressures higher In some of the experiments, the reactor section was than 12,000 pounds per square inch are not only operpeeked Wlth PP PuIlehihgS other material, Whereas able but may be advantageous from the standpoint f in other experiments, the reaction zone was empty. Also, increased yields and selectivity of the reaction. Consea pp hhef Was uSed 1n the reactor in some of the quently, the foregoing pressure ranges are to be taken as experiments whereas an unlined stainless steel reactor indicative of the general range throughout which our Was used In other of the experiments- The thermocouple condensation reactions i l b b i d cover was in some instances covered with copper. Cop- The temperature at which our process is onducted i per 18, of course, a noncatalytic substance in this reaction. dependent to a certain extent upon the reactants em- The Ptlhelpal Prothlete recovered in the experiments were l L F example, h an lk l i h d identified by means of boilmg point, index of refraction, carbon such as toluene, ethylbenzene, or normal propylehethleZtl tests, and y Comparing the infrared Spectrum of benzene is being condensed with an olefinic hydrocarbon the Product With Samples of known eompoundsthe such as ethylene or propylene, a reaction temperature of letter P p hllmher of P Compounds for which about 400 C. or greater ordinarily is necessary to obtain lettered Spectra were unknown, had to be synthesizedappreciable yield. However, when the alpha carbon atom Example I gfghe aromtatic ccgrnpound has altltaclifd there an aetlve The experiments shown in the following Table I were y togen a t e Iefletlon W1 to e Place ePP made to determine the effect of various contacting media y lower temperatilres- In general, the reacnon upon the reaction of ethylene with toluene. In Run 1, no peramres p y In our process W111 be In excess of contacting media was used. In all of the experiments about 350 C. and as hereinbeiore stated, will not exceed except No. 4, a copper liner was employed. In experi- 500 C. at WhlCh point extensive thermal decomposition ment 4, a stainless steel reactor was used without a lining. TABLE I [Toluene-kethylene (3.0 1 mol ratio) in the presence of various contacting media at 450 0., 12,000 p. s. 1., Q1250 HLSVJ Run Number 1 2 3 4 5 6 7 8 Oontactmg Agent None SiOz-AlzOs Quartz St. Steel S101 A1501 Ohar. Cu

Aromatic Chgd CH8 CH2 CH3 CH3 050E; CH1 050E: CH3 Gms 256. 1 266. 0 294. 6 278. 9 291. 6 221. 9 279. 3 314. 0 Mol 2. 78 2. 89 3. 20 3. 03 3. 17 2. 41 3. 04 3. 41 Olefin Chgd C2: C2= O C2= Cz= Gg= C1= Cz= Grns 26.0 27.0 30. 4 27. 9 27. 8 21. 8 27. 0 32. 1 Mols o. 93 0. 97 1. 09 1. 00 0. 99 0. 78 0. 96 1. 15 MoI R 3.1;10 Aromatic to Olefin- 3; 0/1 3. 0/1 3. 0/1 3. 0/1 3.2/1 3.1/1 3.2/1 3. an Experimental Conditions:

Furnace Temperature 462 362 457 456 459 462 461 462 Contact Temp 0. 449 352 451 455 450 450 450 451 Pressure, p. s. 1.. 11,960 12. 090 11, 990 12,100 12, 000 11,980 12,020 12,050 E1.L.S. 2.38 2.40 2.42 2.28 2.60 2.2 2.36 2.50 Llqllld Product, Gms 279. 292.4 322.7 303.9 317.0 243.7 302.5 346.0 Olefin Recovered:

G 0.5 0.5 0.9 0.5 0.3 0.3 0.1 0.8 1.9 1.9 3.0 1.8 1.1 1.4 0.4 2.4 219. 0 182. 4 255. 8 242. 7 257. 2 200. 8 250. 8 271. 8 s5. 5 68. 6 86. 8 8 88. 2 90. 5 89. 8 86. 7 0. 91 0. 94 1. 06 0. 98 0. 98 0. 77 0. 96 1. 12 25. 5 26. 5 29. 5 27.4 27. 5 21. 5 26.9 31. 9 0. o. 91 0. 42 0. 39 0. 37 0. 23 0. 31 0. 46 Grns 37. 1 83. 6 38. 8 36. 2 34. 4 21. 1 28. 5 42. 0 Mols of Aromat1c Reacted per M01 01 Olefin 0. 44 0.97 0. 40 0. 40 0.38 0.30 0.32 0. 41 Composition of product Resulting from:

1 M. olef.+1 M. aromatic- G 24. 0 82.1 27.3 h 23. 9 a 25. 3 d 20. 4 23 5 36. 3 0. 20 0. 68 0. 23 0. 20 0. 21 0.17 0 20 0. 30 glefin r sc gedfl u 23. 2.; 20.0 21.5 22.1 20.8 26.7 roma 1c eac e 5 "1.3 56. 8 2 M. olef.+l M. aromatio- 0 Y 73 g 64 5 65 3 l 1 6 1 1 i7 3 14. 5 11.2 7.2 9.7 8.3 05 0. 0 0.08 0. 5 Mol percent based on total- 0 0 07 0 06 Olefin reacted 24. 2 21.2 22. 6 20.0 16. 3 13. 0 14. 6 10. 7 Aromatic Roasted 26.5 11.0 28.6 25.6 21.6 21.7 22.6 13.0 Aromatic Conversion, Percent. 14.5 31. 4 13. 2 18. O 11.8 9. 5 10. 2 13. 3 Olefin Conversion, Percent 98. 1 98.1 97.0 98. 2 98. 9 98. 6 99. 6 97. 6 Yield Based on Aromahc Conversion. 76. 5 85. 7 83. 3 76.9 78. 4 95. 6 87.1 78.3 Yield Based on Olefin Conversion 46. 2 93. 6 44. 3 40. 0 37. 8 35.1 35. 4 37. 4

Predominantly disubstitnted benzege compounds (Infrared analysis).

I 8% disubstituted benzene compoun s. 9 5% disubstituted benzene compounds. 4 9% disubstituted benzene compounds.

The experiments in which copper pellets were used, in which quartz chips were employed as the packing, and in which stainless steel turnings were used in the stainless steel tube, produced results which were essentially the same as those obtained in Experiment 1 in which no packing was used in a copper lined reaction tube. The presence of copper pellets appears to make the reaction somewhat more selective. These results may be summarized as follows:

Side chain alkylation took place with no nuclear alkylation and over 97% of the ethylene reacted. The yield of CsHra hydrocarbons produced amounted, on the average, to about 21 mol per cent based on ethylene reacted, and to about 50-65 mol per cent based on the toluene reacted. These hydrocarbons consisted of 80-90% of n-propylbenzene and 4-9% of isopropylbenzene. In each of the experiments, about 20-24 mol per cent hydrocarbons, based on aromatic reacted and corresponding to amylbenzenes, were produced. The total weight per cent yield based on aromatic conversion amounted to about 80%, and the total weight per cent yield based on olefin conversion amounted to about 40%. The contacting media removed from the reaction zone at the end of the experiments were clean and not covered with any carbonaceous material.

Very similar results were obtained with charcoal as the contacting media at 450 C. Of course, the amount of carbon formation when charcoal is used, is indeterminate. Here again, side chain alkylation took place and the composition of the Cal-I12 hydrocarbons was over 90% n-propylbenzene.

As expected, the silica-alumina catalyst employed in Experiment 2, induced the reaction of ethylene with toluene at 352 C. More than 98% of the ethylene charged reacted. The yield of CsHio and CQHIZ hydrocarbons amounted to 72 mol per cent based on ethylene reacted and 75 mol per cent based on toluene reacted. The main reaction was nuclear alkylation.

form ethylbenzenes and xylenes.

about 36% 8 cipal products consisted of ethyltoluenes, the composition of which was about 17% ortho, 55% meta, and 28% p-ethyltoluene. The CaHm hydrocarbons were composed of ethylbenzene and xylenes. The formation of xylenes and ethylbenzene is probably due to an alkyl transfer reaction, which probably proceeded through disproportionation of toluene into xylene and benzene, the latter then reacting with ethylene to form ethylbenzene or through the interaction of ethyltoluene with toluene to The recovered toluene fraction also contained benzene. After the reaction, the catalyst was black; it contained 1.6% carbon. Since silica-alumina is a well-known nuclear alkylation catalyst, this experiment shows that when known aromatic alkylation catalysts are employed, under the operating conditions used in our process, the main reaction is nuclear alkylation; side chain alkylation is not obtained. Accordingly, our invention is carried out in the absence of known alkylation catalysts.

Alumina and silica were individually evaluated as contacting media. In the presence of these materials, side chain alkylation was the principal reaction. The CaHrz compounds, amounting to 22 mol per cent based on the ethylene reacted, and 55-75 mol per cent based on the toluene reacted, were composed of about 90% n-propylbenzene, along with isopropylbcnzene and a small amount of m-ethyltoluene. The weight per cent yields based upon the toluene reacted range from 78-96%, and the weight per cent yields based upon olefin reacted are After reaction, the alumina was light gray; whereas the silica gel was black.

Example 11 The results obtained when condensing toluene with six different olefins including ethylene, propylene, l-decene, l-dodecene, cyclohexene, and methylcyclohex- The prmone, are shown in the following Table II.

TABLE II [Toluene various olefins (3.0:1) in the presence of copper pellets at; 450 0., 12,000 1). s. 1., and=2.50 HLSVJ Run No 9 10 11 12 13 14 Contacting Agent.-. Cu Cu Cu Cu Cu Cu 450E; oCH; 50E; SCHt CH1 30H, 314. 0 425. 0 291. 1 111. 4 303. 2 293. 4 3. 41 4. 62 3. 16 1. 21 3.30 3. 19

cycle Methyleyclo- Ca= Cz== 1-Cio= 1-C1r= Co= C|= 32. 1 64. 8 147. 8 67. 8 90. 3 101. 6 Mols 1. 15 1. 54 1. 06 0. 1. 1. 06 M01 Ratio Aromatic t0 Olefin 3. Oil 3.1/1 3.0/1 3. 0/1 3.0/1 3. 0/1 Experimental Conditions:

Furnace Temp, C 462 461 462 461 461 470 Contact Temp, C 451 4 451 450 450 Pressure, p. s. i.-. 12, 050 12,060 11, 990 12,000 12,020 11,840 H. L. S. V 2. 2. 2. 2.22 2.4 2.42 Liquid Product, Gms. 346.0 485 5 429.9 178.0 413.9 407.1 Olefin Recovered- 271. 8 374. 3 259. 7 99. 1 294. 8 282. 3 86. 7 86. 7 89. 3 89. 0 97. 2 06. 2 1. 12 1. 151 0.94 0. 29 0.18 0.18 31. 9 63.0 131. 3 48. 4 14. 7 17. 0 0. 46 0. 56 0. 34 0. 13 0. 10 0. 12 Gms 42. 0 51. 0 31. 4 12. 3 8. 4 11. 1 Mols of aromatic reacted per mol of olefin 0. 41 0.37 0. 3B 0. 47 0. 56 0. 67 Composition Of Product Resulting from:

1 M. olef. 1 M. aromatic- G 8. 3 17. 6 20. 5 Mols. 0. 06 0. 10 0. 06 Mol. Percent Based on Total Olefin Reacted l0. 7 13. 2 34. 4 aromatic Reaetei. 13.0 17.9 38. 5 Aromatic Conversion, Pereent 13.3 13. 3 10. 7 11.0 2. 8 3. 8 Olefin Conversion, Percent. 97. 6 97. 1 88. 9 71. 4 16. 4 16. 7 Yield based on Aromatic Conversion 78.3 82. 2 91. 2 77. 0 96.0 100 Yield based on Olefin Conversion 37. 4 37. 2 33. 0 51. 6 53. 3 66. 7

(-)May contain some dicyelic hydrocarbons.

The product resulting from the condensation of one molecule of ethylene with one molecule of toluene consisted of 90-95% of n-propylbenzene and -10% of isopropylbenzene. The product resulting from the condensation of two mols of ethylene with one mol of toluene consisted primarily of n-pentylbenzene. The weight per cent yield based on toluene conversion was 78.3%, and on ethylene conversion was 37.4%.

The product resulting from the condensation of one molecule of propylene with one molecule of toluene consisted of approximately 90% n-butylbenzene and 10% isobutylbenzene. The weight per cent yield based on toluene conversion was 82.2%, and on propylene conversion was 37.2%.

The elfect of operating variables upon the side chain alkylation of toluene with ethylene was investigated. The pressure range covered in this investigation was 3000- 12000 p. s. i.; the temperature range was 375-450" C.; and the-liquid hourly space velocity range was 0.7-2.5. The results obtained are given in Table III.

TABLE III Toluene-i-ethylene (3.0:1) in the presence of copper at 375450 0., 3000-12000 p. s. i., and 0.66-2.50 HLSVJ Run No 16 17 18 19 20 Contacting Agent On On Cu Go On Cu Aromatic charged 0H, 0151; .3011: oOH; CH3 OH1 Gms 314. 0 252. 3 257. 2 314. 8 304. 0 228. 8 Mols 3. 41 2. 74 2. 80 3. 42 3. 2. 49 Olefin eharged C1: Cg= C1: O1= Cz= C2= Gms 32. 1 24. 6 26. 9 31. 1 29. 6 23. 6 M015 1. 15 0. 88 0. 96 1. 11 1. 06 0. 84 M01 Ratio Aromatic to Olefin 310/1 3.1/1 2. 9/1 3. 1/1 3. 1/1 3. 0/1 Experimental Conditions:

Furnace 'Iemp., C 462 410 386 460 412 412 Contact Temp C 451 401 376 450 400 400 Pressure, p. s. 12, 050 11, 980 12,000 3, 100 3,100 3, 100 H. L. S. 2.50 2. 34 2. 46 2.44 2.46 0.66 Liquid Product, Gm 346.0 271. 6 269. 4 341. 5 315.0 246. 7 Olefin Recovered:

271. 8 228.0 244. 6 278. 9' 289. 5 209. 2 86.7 90. 4 95. 1 88. 6 95. 2 91. 4 11 12 0. 70 0. 44 0. 98 0. 44 63 31. 9 19.6 12. 2 27. 5 12.2 17. 6 0. 46 0.26 0.14 0.39 0.16 0. 21 ms 42. 0 24. 3 12. 6 35. 9 14.5 19. 6 Mols of Aromatic Reaeted per M01 01 0lefin 0. 41 0. 37 0. 33 0.40 0.36 0. 33 Composition of Product Resulting from:

1 M. 0let.+1 M. aromatic- G1ns 36. 3 12.0 3. 9 27.0 3. 6 11. 6 M0ls 0. 30 0. 10 0. 03 0.23 0.03 10 M01 per 111: based on total Olefin- Reacted 26. 7 14. 3 6. 8 23. 5 6. 8 15. 9 Aromatic Reacted 65. 3 38. 5 21. 4 57. 5 18. 7 48. 6 2 M. olef.=1 M. aromatic- Gms 8. 3 8. 9 3. 1 12. 6 2.0 9. 2 M015 0. O6 0. 06 0. 02 0. 09 0. 01 06 Mo] percent based ontotal- Olefin Reacted 10. 7 17.2 9. 1 18. 4 4. 5 19.0 Aromatic Reacted 13. 0 23. 1 14. 3 22. 5 6. 3 28. 6 Aromatic Conversion, percent. 13. 3 9. 6 4. 9 11.4 4.8 8. 6 Olefin Conversion, percent 97. 6 79. 7 45. 4 88. 4 41. 2 74. 6 Yield based on Aromatic Conversion. 78. 3 61. 1 35. 7 80.0 25.0 77. 2 Yield based on Olefin Conversion 37. 4 31. 5 15. 9 41. 9 11.3 34. 9

The principal products formed in experiments 11 and 12 in which the olefins were l-decene and l-dodecene respectively were undecyl-, and tridecylbenzene. The re-. action is somewhat more complicated than the reaction in which a lower boiling olefin was utilized. This is shown by the fact that some lower boiling alkylbenzenes are formed. High molecular weight alkylbenzenes also are formed. A portion of the tridecylbenzene was sulfonated, neutralized with sodium hydroxide, and evaluated as a detergent. It was found that the detergency of the resulting sulfonate was greatly superior to the standard, Nacconol NR. It is believed that detergents of this type are new compositions of matter, inasmuch as the alkyl group contains no branching whatsoever. Thus, it can be seen that one of the principal advantages of our process is that it affords a direct method for producing alkylbenzenes in which the alkyl group is a straight chain, said compound being convertible into superior surface active agents.

The reaction of alkylaromatic hydrocarbons such as toluene with cycloolefins appears to be somewhat. more diflicult than the reaction with aliphatic olefins. For example, in experiment 13, 83.6% of the cyclohexene was recovered. Of the 16.4% of the cyclohexane that reacted, only about 50% underwent the desired types of These data indicate that as the reaction temperature is lowered at a given pressure and space velocity, the extent of both aromatic conversion and olefin conversion decreases. A deleterious eflect'of this lower conversion can also be noted on the yields based upon the conversions; Lowering the pressure from 12000 p. s. i. to 3000 p. s. i. while maintaining a constant temperature and space velocity, has very little efiect upon conversion and yields. At 3000 p. s. i., a decrease in temperature at a constant space velocity results in lower conversions and yields. This drop in conversion and yield can be overcome by a decrease in space velocity as demonstrated in Experiment. 20 wherein the space velocity was cut about 3.5 times and this just about compensated for a 50 C. decrease in reaction temperature.

Example IV velocity of about 2.35. The results are summarized in.

Table IV.

2,758,140 12 At35 1 C., only 37%, of the ethylene reacted yielding mostly polymeric hydrocarbons. Less than 1% of the aromatic hydrocarbon charged, reacted. At higher 1 115 5 47 8 6 762 3 -4.3 m8 A m 8 TABLE IV (3.03) in the presence 01 charcoal at 350-450" (3., 12, p. s. i. and 2.50 HLSVJ [Toluene ethylene 13 Experiments 24 and 25 were carried out at 12000 p. s. i. and at 21 mol ratio of toluene to propylene of 3.1/1 in 14 TABLE VI [TolueueJ-l-decene at various mol ratios 425-450" 0, 12,000 p. s. 1., :42.50

one case and 9.7/1 in another. Aromatic conversion was i t e presence f c ppe pellets] decreased by 1ncreas1ng the mol ratio. The same ob- 28 29 servatlon can be made for olefin conversion. The weight 5 Contacting Agen Cu Ou per cent yields based on aromatic conversion decreased with increasing mol ratio.

At a constant higher mol ratio of approximately 10.0/1 the effect of lowering the pressure from 12000 to 6000 p. s. i. was noted by comparing experiments 25 and 26. 1 be 1 k6 The conversions and yields were not affected materially 1c efin 3.0/1 10.'1/1

n Experimental Conditions: by thb drop m pfessure' Furnace Temp., C' 462 440 At 6000 p. s. 1., a further 1ncrease 1n mol ratio was Contact'lempt, 0. 451 426 made from :1 to about :1. Ihis further increase in 28 22 mol ratio again decreased both aromatic and olefin con- 15 Liquid Product, dine -II IIIII 429.9 1333.3 version, but here some beneficial effect on the yield of Rmvered 16 5 59 0 desired products seems to be obtained. 11:1 15 Example VI 259.7 1054.8 The effect of operating variables upon the side chain 8%: 3 alkylation of toluene with l-dodecene was investigated. 3 1% The pressure in this investigation was held constant at ms 1 h 12000 s. i. the hourl li uid s ace velocit was held M916 of Aromatic Reacfed p M91 r efin 0.36 1.35

t t th t y i p d Composition oiP'roduct Resulting from: cons an a e empera re was vane 111 e range 1 L+1 a. of 425-450 0., and the mol who of aromatic to olefin 0 5 32 BS- i was varied from 3.0/1 t o 10.1/1. A summary of the fia-5555555535}5} results observed 1s given 1n Table VI. 2 E

gg-g At 450 0., 12000 p. s. 1., 2.4 HLSV, and with an i, 3 Jam g aromanc to olefin mol who of 3.0, the aromatic conversion g a was 10.7%, and the olefin conversion was 80.9% The g;5g '55gga'5h" weight per cent y1eld of desired 1/1 condensation product glz fi gg was 91.2% based on the aromatic reacted, and 33.0% Aromatic ooneersiofi, ,5,3 i 33 "5 13 based on the olefin reacted. When the temperature was gl i gggfi g gg gffg g g-g decreased f to and the aromatic o fin yifito based on Olefin 0311943101.; 1 3310 4413 mol ratio ra1sed to 10.1/ 1, a decrease in aromat1c con TABLE VII [Toluene+l-d0decene (3.010 mol ratio), 400-475 0., 3000-12000 P. s. i., 0.5-2.5 HLSV, and in the presence of copper pellets] Run N0 30 31 32 33 34 35 36 37 38 39 40 Contacting Agent Cu St. Steel 011 011 Cu Cu 011 611 Cu On St. Steel Aromatic Charged Toluene Toluene Toluene Toluene Toluene Toluene Toluene Toluene Toluen Toluene Toluene Gms 11 .4 206.1 173.1 198.5 240.8 215.4 232.2 207.2 166.3 117.9 174.2 Mols 1. 21 2. 24 1. 88 2. 16 2. 2. 34 2. 52 2. 26 1. 81 1. 28 1.89 Olefin charged 1-C1:= 1-C1;= 1-C11= 1-C13= 1-C1g= 1-cn= 1-C1z= 1-C1z= 1-C g== 1-C z= l-C g= Gms 67. 8 125. 5 105.3 120.5 146. 5 131. 0 141. 4 126. 1 101. 2 71. 7 106. 1 Mols 0. 40 0. 75 0. 63 o. 72 0. 87 0. 78 0. 84 0. 75 0. 0. 45 0. 63 Mel Ratio Aromatic t0 Olefin 3.0 1 3.0/1 3.0/1 3.0/1 3.0/1 3.0/1 3.0/1 3.0/1 3.0/1 3.0/1 3.0 1 Experimental Conditions:

Furnace Temp., 461 461 433 411 460 492 462 461 460 465 460 Contact Temp, 0.. 450 456 4 401 453 479 451 450 450 451 000 Pressure, 0.5. i. 12,000 12, 000 12,000 12,000 6,130 3,000 3,000 3, 070 3,000 3,070 0,000 B. L. s.v 2.22 2.76 2.34 2.52 2.40 2.40 2.26 1.34 0. 0.52 0.50 Liquid Product, Gms 178.0 336.0 291.1 325.0 391.0 340.4 372.5 332.0 263.8 192.3 280.8 Olefin Recovered:

G 19.4 6. 8 17. 0 61. 4 13. 1 10. 5 24. 2 21. 1 11. 7 10. 1 14.3 28.6 5.4 16.1 51.0 8.9 8.0 17.1 16.7 11.6 14.1 15.5 Aromatic Recovered:

Gms 99.1 175.4 158.7 190.9 209.6 188.7 212.3 180.4 144.2 102.1 151.0 Percent 89.0 85.1 91.7 96.2 87. 0- 97.6 91.4 87.1 86.7 86.6 86.7 Mols 01 Olefin Reacted. 0. 29 0. 707 0. 526 0. 352 0. 794 0. 717 0. 0. 496 0. 533 0. 367 0. 546 Gms 48. 4 118.7 88. 3 59. 1 133. 4 120. 5 117. 2 105. 0 89. 5 61. 6 91. 8 Mols of Aromatic Reacted 0.13 0. 334 0.157 0. 083 0. 339 0. 29 0. 216 0.14 0. 24 0.172 0.252 Grns 12. 3 30. 7 14. 4 7. 6 31. 2 26. 7 19.9 26.8 22. 1 15. 8 23. 2 Mols oi Aromatic Rcacted per M01 or Olefin 0.47 0. 47 0.30 0. 24 0.43 0. 40 0.31 0 28 0. 45 0. 47 0 46 Composition of Product Resulting from:

1 M. olef.-l-1 M. Aromatic- Gn1s 11. 7 23. 8 -27. 6 -13. 6 31. 1 -27. 5 30. 9 34. 2 24.9 17. 1 19. 3 Mols 0. 05 0. 092 0. 106 0. 052 0. 12 0. 016 0. 119 0. 132 0. 096 0. 066 0. 074 M01 percent based on total- Olefin reacted..- 17.2 13. 0 25. 4 14. 9 16. 1 14. 8 17.0 26. 0 18.0 17.9 13. 6 Aromatic reacted 38. 5 27. 5 67. 5 62. 7 35. 4 36. 6 55. 0 94. 3 40. 0 38. 8 29. 3 2 M. olef.+l M. aromatic- Gms 20.5 Mols 0.05 M01 per cent based on total- Olefin reacted- 34. 4 Aromatic reacted 38. 5 Aromatic Conversion, percent 11.0 14.9 8. 3 3. 8 13.0 2. 4 s. 6 12. 9 13.3 13. 4 13. 3 Olefin Conversion, percent 71. 4 94. 6 83. 9 49. 0 91. I 92. 0 82. 9 s3. 3 88. 4 85. 9 86. 5 Yield based on Aromatic Conversion 77. 0 27. 5 67. 5 62. 7 35. 4 36. 6 55. 0 94. 3 40. 0 38. 8 29. 3 Yield based on Olefin Conversion 51. 6 13. 0 25.4 14.9 15. 1 14.8 17.0 26. 6 18. 0 17. 9 13. 6

- Contains some olefinic compound; probably unsaturated alkylate. b 3.8 g. oleflnie; probably unsaturated alkylate.

15 version and in olefin conversion was experienced. The weight per cent yield product based on aromatic conversion also decreased. From these results it appears that a decrease in yield as is caused by a decrease in tempera- 16 Experiments 30, 34,-and 36, show the effect of decreasing pressure with these reactants. Olefin conversion remains high throughout while at 3000 pounds, there appears to be some decrease in aromatic conversion.

ture cannot be satisfactorily overcome by raising the mol The yields of desired products appear to be more selective ratio of aromatic to olefin utilized. at the higher pressure condition in this case.

Example VII Experiments 35 and 36 show the efiect of increased temperature in which the aromatic conversion is de- The effect of operat ng variables on the side cha creased. Raising the temperature of the reaction under alkylation of toluene with l-dodecene at an aromatic to these conditions f to C appears to olefin mol ratio of 3. 1 was nvestigated. The pressure make the reaction less selective. Tanga covered In thls mvestlgatlgn 3 07 ii {5 Experiments 36, 37, 38, 39, and 40 illustrate the effect g tlemperaturelragge was 400 g the qm of lowering the liquid hourly space velocity while holding our Y Space ve f i summary other conditions constant. Olefin conversion remains of the data obtamed 1s gwen m Table about constant throu hout but higher aromatic conver- Esperiments 30 and 31 are the same, carried out at a e btai d 1 1 12.000 p. s. i., 450 C., and approximately 2.5 HLSV, 31 Be Wg a 1 space v6 0m except that in Experiment 30 the reactor was lined with e Welg per can f s ase on copper and filled with copper pellets, whereas in Experiand 9 9 Fonversmn appear very slmllar Over ment 31 an unlined stainless steel reactor filled with the entll'511qu1d hourly p c Velocity range. stainless turnings was used. It will be noted that based E 1 VIII upon the weight per cent yields, the conversion in the p ramp 8 presence of copper seem to be much more clearcut than T efiect er a u those which take place in the presence of stainless steel. alk iz of g zg i i E g i Side fi i Experiments 32 and 33 are carried out similarly except l g 1 f 81 1 o 2 l l 1c 0 for a decrease in reaction temperaturefrom450 C. to o e n m0 Ta 10 0 V l t T e pres- 0 in the latter It will be noted that the sure range covered in this investigation was 300012,000 aromatic conversions drop ofif as the temperature is P- temperature range was 425L475, 6 and lowered and that the yields based on aromatic converhquld hourly Space veloclly range was A sion and on olefin conversion are lowered as the temperaa y of the data Obtained are Presefltfid 111 Table tures are lowered. VIII.

TABLE VIII [Toluene l-dodecene (10011.0 mol ratio), 425-475 0., 3,000-12,009 p. s. i., 0.5-2.5 HLSV, and in the presence 0! copper pellets] Run No 41 42 43 44 45 46 47 48 49 50 51 Contacting Agent On On Cu Cu 011 u u u Cu Cu Cu Powder Aromatic Charged Toluene Toluen Toluene Toluene Toluene Toluene Toluen Toluene Toluene Toluen Toluene Gms 1010.4 844.2 840.9 808.8 830.1 822.4 767.6 323.3 871.8 846.5 744.5

10.98 9.18 9.14 8.79 9.02 8.94 8.34 3.50 9.48 9.20 8.09 I-O12= n= 1-C19= 1-C1z= 1-012= 1-Cn= 1- n= 1-C1l= 1-C1:= 1-C1:= 1-C1:= 184.5 154.1 153.5 147.7 151.6 150.2 140.2 58.8 159.2 154.6 136.0 Mols 1. 10 0. 92 0. 91 9. 88 9. 9. 89 0.83 0. 35 0. 0. 92 0. 81 M01 Ratio Aromatic to Olefin 10.0/1 10. 0/1 10. 0/1 10. 0/1 10. 0/1 10. 0/1 10. 0/1 10. 0/1 10. 0/1 10. 0/1 10. 1/1 Experimental Conditions:

Furnace Temp, 461 440 483 466 460 457 428 432 462 Contact Temp., C 450 426 474 453 448 451 423 425 454 Pressure, p. s. 12,130 12, 060 6,030 6, 030 6, 040 5, 990 6, 070 6,040 2,980 3,060 H. L. s. V 2.40 2.40 1.73 1.78 1. 0.91 0.88 0.36 1.24 1.20 0.59 Liquid Product, Gms 1211.2 1010.4 1014.4 974.0 1003.5 996.9 921.4 383.8 1038.7 1012.1 881.8 Olefin Recovered:

Gms 22. 4 50. 6 11. 5 22.3 32. 3 14. 4 33. 7 7. 7 27. 1 31. 0 13. 6 Percent 12. 1 32. 8 7. 1 15. 1 21. 3 9. 6 24.0 13. 1 17.0 20. 1 10. 0 Aromatic Recovered:

Gms 918.7 787.6 791.2 753.1 779.3 770.4 727.8 297.5 820.9 801.4 684.7 Percent 90. 9 93. 3 94. 1 93. 1 93. 9 92. 5 94. 8 92. 0 94. 2 94. 7 92. 0 Mols of Olefin Reacted- 0.965 0. 516 0.845 0. 746 0.71 0.808 0.034 0.304 0.786 0.736 0.729

ms 162.1 108.5 142.0 125.4 119.3 135.8 106.5 51.1 1321 123.6 122.4 Mols of Aromatic Reaoted... 0. 997 0. 615 0. 54 0. 605 0.552 0. 674 0. 433 0. 28 0. 553 0.49 0. 65 Gms 91. 7 56. 6 49. 7 55. 7 50. 8 52. 0 39. 8 25. 8 50. 9 45. 1 59. 8 Mols of Aromatic Reaeted Per M01 or Olefin 1. 03 1.00 0. 64 0.81 0. 78 0. 83 0. 68 0. 92 0. 70 0.67 0. 89 Composition of Product Resultlng from:

1 M. olef. 1 M. aromatic- Gms.-- 86. 6 57. 3 34. 4 58. 2 58. 0 57. 1 58. 1 27.0 43. 1 54. 7 34. 3 Mols. o. 333 0. 22 0. 132 0. 224 0. 223 0. 22 0. 223 0. 104 0. 0. 21 0. 132 M01 per on total- Olefin reacted. 34. 5 35. 7 15.6 30. 0 31. 4 27. 2 35. 2 34. 2 21. 0 28. 5 18.1 Aromatic reacted a3. 4 35. 8 24. 4 37. o 40. 4 32.6 51. 5 37. 1 29. 8 42.8 20. 3 2 M. olef. l M. aromat- Gms Mols M01 percent based on tot Olefin reacted--- Aromatic reacted Aromatic Conversion, percan 9.1 5. 7 5. 9 6. 9 6.1 7. 5 5. 2 8. 0 5.8 5.3 8. 0 Olefin Conversion, percent 87. 9 67. 2 92.9 84. 9 78. 7 90. 4 76.0 86.9 83.0 79.9 90. Yield based on Aromatic Conversion 33. 4 35. 8 24.4 37.0 40.4 32. 6 51. 5 37.1 29. 8 42.8 20.3 Yield based on Olefin Conversion 34. 5 35. 7 15. 6 30. 0 31. 4 27.2 35. 2 34. 2 21. o 28. 5 18. 1

Experiments 41 and 42 illustrate the decrease in conversions that are obtained at 450 C., 12,000 p. s. i.,

13 3.0/1, 450 C., 12,000 p. s. i., and an hourly liquid space velocity of 2.5 over copper pellets in :a copper lined and 2.4 HLSV when the reaction temperature is lowered reactor.

TABLE IX [Various alkylaromatics+ethylene (23.0:1) at 450 0., 12,000 p. s. i., 2.50 HLSV over copper pellets] Run N 52 53 54 55 56 57 58 59 60 Contacting Agent On On Cu Cu Cu On On Cu Cu /3-Methyl- Ethyl- Sec- C4119 lZ-C4H9 Naptha- Diphenyl- Oyclo Cs- Aromatic Charged Toluene benzene Oumene Benzene Benzene Indan lene methane benzene Gms 314. 0 221. 0 229. 0 265. 4 125. 7 288. 8 174. 290. 1 862. 0 3. 41 2. 09 2. 49 1. 98 0. 95 2. 45 1. 23 1. 73 2. 26 Cz= Cz= C2= C2= C2= C2= C2= Cz= C2= 32.1 20. 5 23. 2 28. 7 11.7 23. 2 11.2 15.8 24. 5 1. 0. 73 0.83 1.02 0.42 0.83 0. 0. 56 0. 875 M01 Ratio Aromatic to Olefin 3. 0/1 29. /1 3. 0/1 1.9/1 2.3/1 3. 0/1 3.1/1 3.1/1 2.6/0 Experimental Conditions:

Furnace Temp, C 462 462 437 467 462 463 460 464 Contact Temp., C 451 4 425 452 451 452 450 452 451 Pressure, p. s. i. 12,050 12, 000 12, 060 12, 010 12, 050 12, 050 11, 950 11, 970 12, 000 L. 2. 2.4 2.: 2.4 2.52 2.38 3 36 3. 2. 47 Liquid Product, Gm 346.0 240.0 319. 5 311. 7 137.5 317.5 2 .7 304. 2 381.6 Olefin Recovered:

Gms 0.8 0. 6 2. 5 0.4 E. 9 1.0 1.1 0.4 0. 49 Percent 2. 4 2. 9 10. 4 1. 4 50. 3 4. 3 9. 8 2. 5 2. 0 Aromatic Recovered:

Gms 271. 8 184. 0 265. 5 211. 6 123. 1 215. 2 158. 8 262. 1 302. 0 Percent 86.7 83. 3 89.8 79. 8 97. 2 74. 5 91.0 90. 3 83. 4 Mols of Olefin Reacted. 1.12 0.71 0.74 1. 01 0.21 0.79 0.361 0.55 0.857 ms 31. 9 19. 9 20. 7 28.3 5. 8 22. 2 10. 1 16. 4 24.0 Mols of Aromatic Reacted 0. 46 O. 35 0. 28 0.402 0. 03 0. 625 0. 111 0. 17 0. 385 Gms 42.0 37. 0 33. 5 53. 8 3. 6 3. 6 15. 7 28.0 60.0 Mols of Aromatic Reacted Per MOI of Olefi 0.41 0. 49 0.38 0.40 0. 13 0. 81 0.31 0. 31 0.44 Composition of Product Resulting trom:

1 M. olei.+1 M. aromatic- 8.3 9.5 6.8 9.1 15.2 0.06 0. 06 0. 04 0. 048 0. 087 M01 Percent based 0 Olefin reacted... 10.7 16. 9 11. 8 9. 5 22.0 Aromatic Reacte 13.0 17. 2 14. 3 12.0 13. 9 Aromatic Conversion, Percent 13.3 16. 7 10. 2 20. 2 2. 8 25. 5 9.0 9. 7 16. 6 Olefin Conversion, Percent. 97. 6 97. 1 89. 6 98. 6 49. 7 95. 7 90.2 97. 5 98. 0 Yield based on Aromatic Conversi 78. 2 82. 8 82. 1 43, 1 100 65 9 42. 4 28. 2 35. 9 Yield based on Olefin Conversion 37. 4 49. 3 37. 5 21. 9 14. 3 63. 2 13.1 8. 7 15.9

25 C. The lower temperature does not seem to result in more selective reaction.

Experiments 43 and 44 (Experiment 45 is a check run on Experiment 44) illustrate diiferences in conversion as the temperature is raised at constant pressure, and space velocity conditions. The further increase in temperature above 450 C. at this pressure, 6000 p. s. i., results in less selective reaction.

Experiments 45 and 46 demonstrate the eifect of space velocity on increased conversion at a given temperature and pressure condition. Here at the lower space velocity the selectivity of the reaction seems somewhat less.

Experiments 46 and 47 demonstrate the effect of lowering the temperature 25 while maintaining the pressure at 6000 p. s. i. and the space velocity at 0.9. The decrease in temperature is accompanied by a decrease in aromatic and olefin conversion and an apparent increase in the selectivity of the reaction. In Experiment 48, the space velocity is dropped again and an increase in conversion is experienced over Experiment 47, apparently compensating for the 25 C. temperature decrease over Experiment 46.

Experiments 49, 50, and 51, were carried out at 3000 p. s. i., and approximately 450 C. Experiments 49 and 50 are check runs while in Experiment 51, copper powder was substituted for copper pellets. The use of the copper powder apparently gives somewhat better contacting for the conversion of both aromatic and olefin is increased over Experiments 49 and 50.

Example IX The data listed in the following Table IX show the results obtained when condensing ethylene with various alkyl-aromatic hydrocarbons in accordance with our process at an aromatic to olefin mol ratio of approximately Representative alkylaromatic hydrocarbons included are toluene, ethylbenzene, cumene, sec-butylbenzene, tertbutylbenzene, indan, fi-methylnaphthalene, diphenylmethane, and cyclohexylbenzene. In each instance, the ethylene conversion was over except in Experiment 5 6 with tert-butlylbenzene where the ethylene conversion was about 50%. The aromatic conversion ranged from 10% to about 25% except in the case of tert-butylbenzene in which the aromatic conversion was low, 2.8%. The weight per cent yields of desired products based upon aromatic conversion are similar to those listed for previous experiments as are the yields based upon olefin conversion.

In Experiment 52, the principal product consisted of 9095% of n-propylbenzene, and 510% isopropylbenzene. The principal product from Experiment 53 is secbutylbenzene. In Experiment 54, the first product was tert-pentylbenzene. Very little condensation of ethylene with tert-butylbenzene was obtained in Experiment 55. This is attributed to the fact that the alpha carbon atom in the side chain of tert-butylbenzene has no hydrogen atoms attached thereto. For this reason, the aromatic compounds that are preferred for use in our process contain a saturated carbon atom attached to a carbon atom of the aromatic nucleus, said saturated carbon atom having at least one hydrogen atom attached thereto.

Experiments 57, 58, 59, and 60 were made with carbocyclic, aromatic compounds having other cyclic rings attached thereto, namely, indan, fi-methylnaphthalene, diphenylmethane, and cyclohexylbenzene. The principal product from the reaction of indan with etheylene was l-ethylindan, i. e., the product formed by condensation of the ethylene group with one of the saturated alpha carbon atoms in the indan molecule. The structure of l-ethylindan was proved by comparison of its infrared absorption spectrum with that of a synthetic. sample prepared by reacting l-indanone with ethyl magnesium bromide to yield l-hydroxy-l-ethylindan, followed by de- 2%] 450 to. 475 (3., pressures of SOD-12,000 p. s. i., and at an hourly liquid space velocity of approximately 2.50 over copper pellets.

TABLEX [Ethylbenzene-l-verious oleflns (x3021 mol ratio), 450 475 0., 500-12000 p. s. i.,z2.50 HLSV and in the presence of copper pellets] Run N o 61 62 63 64 65 66 67 Contacting Agent. Go Go On Cu Cu Cu Cu Aromatic Charged Ethyl- Ethyl- Ethyl- Ethyl- Ethyl- Etbyl- Ethylbenzene benzene benzene. benzene benzene benzene benzene 221. 407. 9 321. 0 377. 6 258. 0 364. 3 354. 2. 09. 3. 85- 3. 03 3. 56. 2. 43 3. 37 3. 28 G1; G1; Cg; Ca C:= GYCIO cyelo Ca= Ca: 20. 5 41. 5 28. 3 34. 9. 34. 0 105. 4 102. 6 LIols 0. 73 1. 48 1. 01 1. 0. 81 1. 29 1.25 M01 Ratio Aromatic to Olefin 2. 9/1 2. 6/1 3.0/1 2. 9/1 3. 0/1 2. 6/1 2. 6/1 Experimental Conditions:

Furnace Temp., C 462. 46]; 463 462 462 461 486 Contact Temp, C. 451 451 452 450 451 450 476 Pressure, 1). s. L.-. 12, 000 3, 010 1, 490 500 3, 200 12,050 12,000 H. L. S. V 2.42 2. 44 2. 60 2. 52 2. 40 2. 2.42 Liquid Product, Gms 240. 0- 44.4.0 337. 5 384. 0 283.0 472.1 456. 6 Olefin Recovered:

Gms 0. 6 2. 2 11.0 27. 9 11.1 76. 8 25. 5 Percent 2. 9 5. 3 34. 8 80. 0 32. 7 72. 9 24. 9 Aromatic Recovered:

Gms 184i 0 354. 0 305. 3 371. 0 234. 0 349. 8. 336. 7 area 83. 3 86. 8 85. 0 98. 6 90. 7 96. 0 95. 0 0. 71 1. 40. 0. 62 0. 25 0. 55 0. 0. 94 19. 9 39. 3 17. 3 7. 0 22 9 28. 6 77. 1 0. 35 O. 51 0. 15 0. 06 0. 23 0. l3 0. l7 Gms 37. 0 53. 9 15. 7 6. 6 24. 0 14. 5 17. 8 Mols of Aromatic Reacted per M01" of Olefirn. 0. 49 0. 34 o. 24 0. 25 0. 42 0.37 0.18 Composition of Product Resulting from:

1 M. olet+1 M. Aromatic- Gms 30. 3 47. 0 18. 6 None 21.0 13. 5 13. 2 Mols 0. 23 O. 35 0. 14 0. 12 0. 07 0. 07 Mo] Percent Based on Total- Olefin Reacted 32. 4 25. 0 22. 5 21.8 20. 0 7. 5 Aromatic Reacted 65. 7 68. 6 93. 4 52. 2 53. 8 41. 2 2 M. olef.+1 M. Aromatic- G 9. 5 17. 7 1. 5 None 9. 0 0. 06 0. 11 0. 01 0. 04

16.9 15.6 3.2 14. 5 17. 2 21. 6 6. 7 17.4 16.7 13. 2 15.0 1.4 9. 3 4. 0 5.0 Olefin Conversion, Percent 97. 1 94. 7 65. 2 20.0 67. 3 27.1 75. 1 Yield based on Aromatic Conversi 82. 9 90. 2 100. 1 0. 0 69. 6 53. 8 41 2 Yield based on Olefin Conversion 49. 3 40. 6 25. 7 O. 0 3d 3 20.0 7. 5

hydration in the presence of oxalic acid and hydrogenation under 100 atmospheres hydrogen pressure in the presence of n-pentane at a temperature of 3050 C. to yield l-ethylindan. This experiment shows that even when the side chain of the aromatic compound is cyclic, rather than aliphatic. the alkyl group attaches to the saturated alpha carbon atom.

In Experiment 58, B-methylnaphthalene was reacted with ethylene. Again, it was established that the ethylene group attached to the methyl side chain. The principal l/l condensation product isolated from the reaction of ethylene with diphenylmethane was LI-diphenylpmpane. With cyclohexyl benzene and ethylene, the l/ l condensation product was l-phenyl-l-ethylcyclohexane.

Example X The results obtained when condensing ethylbenzene with three different olefins including ethylene, propylene, and cyclohexene are shown in Table X. These experiments were carried out at an aromatic to olefin moi ratio of approximately 3.0/1, at temperatures ranging from Experiments 6.1, 62. 63, and 64 were carried out with ethylene at 450 C., approximately 2.5 HLSV, and. with pressure ranging from 50012,000 p. s. i. The decrease in aromatic and olefin conversions with the decrease in pressure. are readily observable. No reaction products were isolated from the experiment at 500 p. s. i.

The results. of the reaction of ethylbenzene with propylene are given in Experiment 65. 52.2% of the ethylbenzene that reacted, combined with 21.8% of the propylene that reacted to yield the desired 1/1 molar condensation product.

Experiments 66 and 67 demonstrate the reaction of ethylbenzene with cyclohexane at 12,000 p. s. i., approximately 2.4 I-LLSV, and with a temperature of 450 C. and: 475 C. The higher temperature results in higher aromatic and olefin conversion accompanied by a decrease in the selectivity of the reaction.

Example XI The results obtained by condensing cumene with two diflerent olefins including ethylene, and cyclohexene are sho n n Table XI.

TABLE X1 [Oumene various olefinsz3.0:1 mol ratio, 375475 0., EGO-12,000 p. s. i.,z2.50 HLSV. and in the presence of copper pe11ets.]

68 69 70 71 72 Cu Cu Cu Cu On Aromatic Charged Oumene Cumene Cumene Oumene Gms. 280.0 233.0 296. 6 425. 9 M s 2. 33 1. 94 2. 48 3. Olefin char Cg= Or= Or= cycle-O11= Gms 21. 6 18. 1 23. 1 97. Mols 0.77 0.65 0. 83 1.18 M01 Ratio Aromatic to Olefin 3. 0/1 3.0/1 3. 0/1 3. 0/1 3. 0/1 Experimental Conditions:

Furnace Temp, C 437 487 487 388 462 Contact Temp, C 425 476 476 375 451 Pressure, p. s. i 12, 060 12, 080 12, 070 12, 040 11, 950 H. L. S. V 2. 36 2.48 1. 2. 28 2.46 Liquid Product, Gms 319. 297. 4 244. 7 308. 5 523.2 Olefin Recovered:

GlIlS 2. 5 0.2 0.3 18.1 57.0 Percent 10. 4 0. 9 1. 4 78. 4 58. 8 Aromatic Recovered:

Gms 265. 5 241. 8 186. 7 278. 6 317. 8 Perc nt 89. 8 86. 5 80.0 93. 9 98. 1 Mols of Olefin Reacted 0.74 0.77 0. 64 0. 18 0.488 20.7 21.4 17.8 5.0 40.0 Mols of Aromatic Reaeted. 0.28 0.32 0.39 0. 0.068 ms 33. 5 38.2 47.0 18.0 8.1 Mols of Aromatic Reacted per M01 of Olefin. 0.38 0.42 0. 61 0. 84 0.14 Composition of Product Resulting from:

1 M. olef. 1 M. Aromatic- Gl'ns 27. 9 25. 0 19. 0 13. 0 9. 9 Mols 0.19 0. 17 0. 13 0.09 0.045 M01 percent Based on total- Olefin Reacted 25. 7 22. 1 20. 3 50. 0 9. 2 Aromatic Reacted 67. 8 53. 1 33. 3 60. 0 66. 2 2 M. Olef. 1 M. aromatic Experlments 70, 68, and 69 illustrate temperature lev- TABLE XII els of 375 C., 425 C., and 475 C. all at 12,000 p. s. i.

Indan a-ious olefins'*-*3.0:1mol atio, 375475 0., 500l2,000 s. i. and approximately 2.4 HLSV. The mereasmg aromatic +V 1 r p x250 HLSV, and in the presence of copper pellets] conversions obtained as the temperature is raised are 40 self-explanatory as are the increasing olefin conversions. Run N0 73 74 The selectivity of the reaction drops 01f somewhat as Contacting Agent Cu 'Cu shown by the yield based on aromatic conversion, and very rapidly as shown by the yield based on olefin con- Aromatic Charged Indan Indan version G-Ins 288. 8 844. 0 M615 2. 7.15 Experiments 69 and 70 demonstrate the etfect of low- Olefin charged C2: 1Ca= ering the hourly liquid space velocity for the reaction of $52 1: 5 cumene With ethylene at 475 C. and 12,000 p. s. i. The 1111401 Ratio ml onatgcfp Olefin 3.0/1 5.0/1

xperimen a 0116111101151 aromatic conversion 1s ncreased by lowering the space Furnace Temp 0 O 463 464 velocity but the selectivity of the reaction seems to be Contact Ternq, O. 452 9 451 decreased slightly. The results obtained by reacting f i f f ffj: IIIIIII'" 2933 2942 cumene with cyclohexene is listed as Experiment 72. Liquid Product, Gms 317.5 1,018.7 The conversion is low and therefore the yield data ques- Recovered" L0 L9 tionable. 4. s 6.8 Example 55 215.2 690.1 .5 1. The operating cond1t1ons and the results of reactmg 3 i indan with ethylene and with l-octene are given in Table 2- 3 ms 73.6 153.9 The results of the reaction of indan with ethylene were M015 01410111200 Rfiacted P6P M Olefin 81 98 0 Composition of Product Resulting irom: previously described in Example IX. The reaction prod- 1 om 1 aromat1c net, as noted there is l-ethylindan. In Experiment 74 5- 2 5 2 indan Was reacted with l-octene to produce l-octylpagggggggga'gggggii indan, which can be converted to a surface active agent Olefin Psfiflcted 365 Aromatic Reacted 52.0 37.4 by sulfonatlon followed by neutralization. 2I I 1ef +1 M aromatic Gms 15.2 26.6 Example XIII MOlS 0.087 0. 078 Mol Percent Based on total- This example was carned out to demonstrate the apglefin gim wd h". 2 15. 11 .5 T011123. 10 6310 e plicabihty of the process of our invention to unsaturated Aromatic conversion, Percent 5 1&2 hydrocarbons contalmng a carbon to carbon triple bond giei i oon ersi n, Pert ent 22.; 23.2 1 SW30 Oll P011131 10 IOHVGISIOH in contrast to the previous examples WhlCh wereall carg bagedon Olefin Conversion 6&2 48-2 ried out with an unsaturated hydrocarbon containing carbon to carbon double bonds. In this experiment a stainless steel reactor was utilized and its internal volume was filled with stainless steel turnings. During the processing period, 312.9 (3.4 mols) of toluene, and 22.1

olefin mol ratio was 6.15/1. 332.2 grams of liquid product was recovered. From this liquid product there was separated no methyl-acetylene and 288.8 grams of toluene, 92.4% of that charged. 5.4 grams of butenyl benzene was recovered. Based on the 7.6% aromatic conversion and the 100% methylacetylene conversion, the weight per cent of the product amounted to 15.4 weight per cent based on aromatic conversion and 7.3 weight per cent based on olefin conversion.

We claim as our invention:

l. A process for producing a side chain alkylatcd aromatic compound which comprises compressing, in the absence of external heating, an unsaturated hydrocarbon and an aromatic compound selected from the group consisting of carbocyclic and heterocyclic aromatic ring compounds having attached to a nuclear carbon atom, a saturated carbon atom to which is attached at least one hydrogen atom, the mol ratio of aromatic compound to unsaturated hydrocarbon being greater than about 1.0, thereafter thermally and noncatalytically reacting the unsaturated hydrocarbon with the aromatic compound at the saturated carbon atom, said reaction being carried out at a pressure greater than about 1000 p. s. i., at a temperature from about 350 to about 500 C., and at an hourly liquid space velocity from about 0.1 to about 10, and thereafter recovering the side chain alkylated resultant product.

2. The process of claim 1 further characterized in that the unsaturated hydrocarbon contains an ethylenic group.

3. The process of claim 1 further characterized in that the unsaturated hydrocarbon comprises an olefinic hydrocarbon.

4. The process of claim 1 further characterized in that said unsaturated hydrocarbon comprises a monoolefin.

5. The process of claim 1 further characterized in that said unsaturated hydrocarbon comprises a monoolefin containing a terminal double bond.

6. The process of claim 1 further characterized in that said unsaturated hydrocarbon comprises ethylene.

7. The process of claim 1 further characterized in that said unsaturated hydrocarbon contains an acetylenic group.

8. A process which comprises reacting an aromatic compound having the following structure:

where A represents a carbocyclic aromatic radical and R is selected from hydrogen and a nonolefinic organic radical attached to the indicated alpha carbon atom through a carbon atom, with a compound selected from the group consisting of olcfinic and acetylenic hydrocarbons, at condensation conditions, the condensation conditions including compressing said reactants containing a molar excess of aromatic compound, in the absence of external heating, thereafter thermally and noncatalytically subjecting said compounds to reaction at a pressure greater than 24 about 1000 p. s i., at a temperature from about 350 to about 500 (3., and at an hourly liquid space velocity from about 0.1 to about 10, to efiect condensation of the unsaturated hydrocarbon with the carbocyclic aromatic compound at said saturated carbon atom.

9. The process of claim 8 further characterized in that the unsaturated hydrocarbon contains an ethylenic group.

10. The process of claim 8 further characterized in that the unsaturated hydrocarbon comprises an olefinic hydrocarbon.

11. The process of claim 8 further characterized in that said unsaturated hydrocarbon comprises a monoolefin.

12. The procms of claim 8 further characterized in that said unsaturated hydrocarbon comprises a monoolefin containing a terminal double bond.

13. The process of claim 8 further characterized in that said unsaturated hydrocarbon comprises ethylene.

14. The process of claim 8 further characterized in that said unsaturated hydrocarbon contains an acetylenic group. i

15. A process for producing side chain alkylated aromatic hydrocarbons which comprises compressing, in the absence of external heating, an unsaturated hydrocarbon and an alkylaromatic hydrocarbon having at least one hydrogen atom attached to the alpha carbon atom, said mixture containing a molar excess of the alkylaromatic hydrocarbon during the reaction, thereafter thermally and noncatalytically reacting said unsaturated hydrocarbon with the alkylaromatic hydrocarbon, at a pressure greater than about 1,000 p. s. i., at a temperature from 350 to about 500 C., and at an hourly liquid space velocity of from about 0.1 to about 10, and thereafter recovering the side chain alkylated resultant products.

16. The process of claim 15 further characterized in that the unsaturated hydrocarbon comprises an olefinic hydrocarbon.

17. The process of claim 15 further characterized in that said unsaturated hydrocarbon comprises a monoolefin.

18. The process of claim 15 further characterized in that said unsaturated hydrocarbon comprises a monoolefin containing a terminal double bond.

19. The process of claim 15 further characterized in that said unsaturated hydrocarbon comprises ethylene.

20. The process of claim 15 further characterized in that said unsaturated hydrocarbon contains an acetylenic group.

References Cited in the file of this patent UNITED STATES PATENTS 2,373,303 Frey et al Apr. 10, 1945 2,448,641 Whitman Sept. 7, 1948 OTHER REFERENCES Sachanen et al., Indust. and Eng. Chemistry, vol. 33, No. 12, pages 1540-1544, December 1941. 

1. A PROCESS FOR PRODUCING A SIDE CHAIN ALKYLATED AROMATIC COMPOUND WHICH COMPRISES COMPRESSING IN THE ABSENCE OF EXTERNAL HEATING, AN UNSATURATED HYDROCARBON AND AN AROMATIC COMPOUND SELECTED FROM THE GROUP CONSISTING OF CARBOCYCLIC AND HETEROCYCLIC AROMATIC RING COMPOUNDS HAVING ATTACHED TO A MOLECULE CARBON ATOM, A SATURATED CARBON ATOM TO WHICH IS ATTACHED AT LEAST ONE HYDROGEN ATOM, THE MOL RATIO OF AROMATIC COMPOUND TO UNSATURATED HYDROCARBON BEING GREATER THAN ABOUT 1.0 THEREAFTER THERMALLY AND NONCATALYTICALLY REACTING THE UNSATURATED HYDROCARBON WITH THE AROMATIC COMPOUND AT THE SATURATED CARBON ATOM, SAID REACTION BEING CARRIED OUT AT A PRESSURE GREATER THAN ABOUT 1000 P. S. I., AT A TEMPERATURE FROM ABOUT 350* TO ABOUT 500* C., AND AT AN HOURLY LIQUID SPACE VELOCITY FROM ABOUT 0.1 TO ABOUT 10, AND THEREAFTER RECOVERING THE SIDE CHAIN ALKYLATED RESULTANT PRODUCT.
 8. A PROCESS WHICH COMPRISES REACTING AN AROMATIC COMPOUND HAVING THE FOLLOWING STRUCTURE: 